Process of manufacturing lubricating oil



Jan. 10, 1933. l R. A. HALLORAN ET A1.

PROCESS OF'MANUFACTURING LBRICATING OIL Filed Nov. 8. 1926 L" NOUN n tIIlIIIIIIIIIPIIn Patented Jan. I0, 1933 UNITED STATES PATENT OFFICE RALPH A. HALLORAN, OF BERKEEEY, AND MARVIN L. CHAPPELL, OF LOS ANGELES, GALIEORNIA,=ASSIGNORS T0 STANDARD OIL COMPANY 0F CALIFORNIA, OF SAN FRANCISCO, CALIFORNIA, A CORPORATION 0F DELAWARE PROCESS OF MANUFACTURING LUBRICATING OIL Application filed November 8, 1926. Serial No. 147,158.

This invention relates to a method of treating unsaturated hydrocarbons, and refers particularly to a method of polymerizing un- .saturated hydrocarbons into higher boiling point oils, suitable for the manufacture of lubricating oils or for other purposes.

When unsaturated hydrocarbon oils are subjected to a reaction with anhydrous aluminum chloride, it is found that two reactions take place. First the unsaturated hydrocarbons are polymerized by the aluminum chloride to form saturated and unsaturated hydrocarbons of higher boiling point, and second the saturated and unsaturated hydrocarbons, either those resulting from said polymerized reaction or otherwise present in the oilmay be decomposed to form a substantially saturated' low boiling point oil or naphtha. The reaction between hydrocar bon oils and aluminum chloride also results in a very material reduction of the sulphur content of the oil. a

There are a number of sources of high sulphur hydrocarbon oils or highly unsaturated hydrocarbon oils, or oils both highly unsaturated and high sulphur bearing, which oils cannot be profitably utilized by the processes now in use to provide refined products such as gasoline or lubricating oil, but find a market solely as fuel oil. For example, certain California asphaltic base crudes yield high boiling point, stocks of excellent body for the manufacture of lubricating oil, but said stock contains such percentages of sulphur as make their refinement impractical. Also there are obtained highly unsaturated oils, for example, the steam still bottoms from naphtha produced by a pressure cracking operation or the oils separating from a sulphur dioxide treatment of petroleum oils, which cannot be profitably treated to form refined products. vAn attempt to subject said highly unsaturated oils to cracking under heat and pressuge results in very rapid 'carbonization' and low yield. v

The object of the present invention is to` provide a method for processing said oils to form low sulphur and more saturated stocks suitable for the manufacture for lubricating oils, or other purposes. More particularly the objectof the present invention is to provide a method of subjecting said oils to reaction with aluminum chloride or equivalent metallic halide under controlled conditions to permit an eiiicient polymerizing and desulphurizing of said oils without permitting an excessive decomposition of the polymerized material into low boiling point voils or naphtha, thus providing a means by which the oils of this type maybe eihciently converted to lubricating oil stocks.

Various further objects and advantages of the present invention will be apparent from the description of the preferred form or example of a process embodying the invention. There is hereafter set forth in considerable detail an example of a process embodying the invention, such as may be carried out by the use of the apparatus illustrated with the accompanying drawing.

In the drawing there is indicated a diagrammatic view of the apparatus, mainly in vertical section.

Referring to the drawing, the preferred K process is conducted therein as follows:

The hydrocarbon oil to be treated, whether of viscous highly unsaturated materials or sulphur bearing constituents or both, or whether a low boiling point oil high in either unsaturated constituents or sulphur bearing compounds, is passed from a suitable source of supply through line 2`by means of a pump 3, and forced' once through a heating coil 4 mounted within a furnace 5, which furnace is indicated as provided with a burner 6.: Within the heating coil 4, the hydrocarbon oil is raised in temperature sufficient to maintain the desired reaction temperature. The reaction temperature to which 'the oil should be heated in the coil 4 depends upon whether a large or small amount of anhydrous aluminum chloride is employed and whether it is desired to produce a material decomposition of the oil. In case sufficient aluminum chloride is used, so that at high temperatures low boiling point oil may be produced, the temperature 4to whichtheV oil' is heated in the coil 1.1. is

say 100 F. Where a small amount of aluminum chloride is used, such as will be mostly expended in strength by polymerizing the oil, somewhat higher temperatures ma be used, such as 450 F. andup to 650 or hi her. The oil passes from the heatin coil 4 t rough a line 6 into a reaction cham r 7. The reaction chamber 7 is indicated as preferably a horizontal cylindrical chamber having an axial shaft 8 passin therethrough which is provided with paddles 9 or other means for scraping the walls of the chamber and agitating the contents therein. Said chamber is also preferably provided near the end opposite to which the hydrocarbon oil enters with a settling or stratifying compartment 10 formed by a baile 11 in the chamber, which bale is preferably provided with one or more openings or perforations 12 near its lower end. The passage of the hydrocarbon oil into the reaction chamber 8 is preferably continuous and at such a rate that the oil may be maintained within the chamber 7 for that period of time desirable in effecting the eiiicient polymerizing reaction.

Within the chamber 7 the oil is continuously contacted with anhydrous aluminum chloride or other equivalent metallic halide in proper proportions to effectv eiicient polymerization of the charge. The amount of aluminum chloride employed will depend considerably upon the character of reaction desired and the character of hydrocarbon oil which it is desired to treat in the process.

Normally the percentage of aluminum chloride will va from approximately .5% to 10% by wei t of the hydrocarbon oil to be converted. n general the polymerization reaction can be performed in two different manners, one in which there is provided only sulicient anhydrous aluminum chloride to efficiently polymerize the oil .without materially decomposing the oil to naphtha, in which case high reaction temperatures such as above 450 and up to 650 F. or higher may be employed; and second, an excess of aluminum chloride over that necessary for the polymerization reaction at high temperatures may be provided, and the reaction confined substantially action by maintaining the temperature below 450 F. and preferably below 300 F. It is understood that in certain cases it is highly desirable for elicient operation and control of the reaction to permit the reaction to proceed with a formation of a certain percentage of low boiling point naphtha, in which case temperatures above 450 F. would normally be em loyed with slightly more aluminum chlori e than is necessary solely for the polymerization reaction.

The aluminum chloride may be continuously or intermittently supplied tothe process in various manners. The preferred manner is by passing the aluminum chloride into the to a polymerization rechamber 7 intermittently from a charger 13 having a valve inlet 14 leading to the chamber 7. In certain cases, however, it may be desirable to admix the aluminum chloride through a line 15 with the feed oil in line 2 before said oil is raised to the reaction temperature, in which case both the aluminum chloride and feed oil may be simultaneously raised to reaction temperature within the heating coil 4 and then conducted into the reaction chamber 7. In certain cases it may be desirable to supply part or all of the heat for the reaction directly to the reaction chamber 7. For this purpose the reaction chamber is indicated as mounted over a furnace 16 provided with a burner or other heat supply means 17.

The material within the reacting chamber 7 may be held under atmospheric pressure or below atmospheric pressure, but it has been discovered that a superior reaction and control of the products is derived through the employment of super atmospheric pressure both on the reaction chamber and on the reux tower or dephlegmator hereafter described. The pressure most desirable is generally between 15 pounds and 80 pounds per square inch, although other pressures may be employed.

lVhen the process is operating to produce polymerization without substantial decomposition of the oil to naphtha, the polymerized oil and resulting tarry aluminum chloride residue is continuously passed from the a tating zone of the chamber into the strati ying compartment 10 where said polymerized oil and aluminum chloride residue stratify. The aluminum chloride residue is then withdrawn through line 18 into a receiver 19 from the lower end of the compartment while the polymerized oil is withdrawn from the upper portion of the compartment through a line 20 and passed to the receiver 21. The withdrawal of these materials may be intermittent but is preferably substantially continuous.

Normally the process proceeds with the roduction of at least a small amount of nap itha and said naphtha is permitted to continuously vaporize and pass through a line 22 into a dephlegmator or reflux tower 23. Therein the vapors are separated from anyaccompanying high boiling point or polymerized oil which is collected within the lower end of the vessel and passed through line 24 into the receiver 21. Any aluminum chloride condensed in the dephlegmator 23 is collected in the bottom of the tower and passed through tar return line 25 again to the reaction chamber 7.

The dephlegmator 23 is indicated as preferably provided at its upper end with an exchanger 26 or other suitable means provided.

ture of the vapors discharging from the dephlegmator may be controlled to form a uniform product. From said exchanger'26 `with a cooling medium by which the temperaor other suitable means the vapors are passed merized oil and the vproduced chlothrou'gh a line 27 to a cooler 28 wherein the produced naphtha is condensed and said naphtha is then-conducted to a na htha receiver 29. The naphtha receiver is indicated as provided with a gas outlet 30 havin a valve 3l and a gauge 32 by which means t e pressure in the system may be controlled.

The process thus described permits a conl saturated constituents o tinuous polymerization and desulphurizing of hydrocarbon oils under conditions to pro- 'duce uniform products and to control and limit the amount of naphtha which will vbe produced to that which will result in the most desirable polymerized oil being produced. The polymerized oil collected in receiver 21 is saturated viscousmaterial readily adapted through processing ,for use as high grade lubricating oil. Sadflubricating oil differs from normal lubrica oils produced either from paran or asp altic base crudes in that'they contain a lhigher percentage of saturated polynaphthenes which possess excellent lubricating properties and having a high resistance to oxidation. l

. While4 the particular process herein described is well adapted to carry out the objects ofpthe inventlon, it is understood that various modifications may be made without departing from the invention, and the invention includes all such modications as comer within the scope of the appended claims.

l. A process of manufacturing lubricating oil, which comprises treating unsaturated oil derived from a sulphur dioxide extract of hydrocarbon oil with aluminum chloride at a temperature suitable for poly- .merizing the oil, and separating the polymerized oil'from the residual aluminum chloride.

2. A process of manufacturing lubricating oil which comprises first heating oil unsaturated derived from a sulphur dioxide extract of hydrocarbon oil, said oil being heated t0 a temperature below 450 F., then contacting the oil with aluminum chloride in a reaction chambery.- applying further heat to the reaction chamber thereby to polymerze the unsaid oil and to produce a relatively small amount of naphtha, and separating said na htha from the polymerized oil and the pro uced aluminum chloride residual.

3. A process of manufacturin lubricating oils from unsaturated hydrocarbons which comprises heating unsaturated lydrocarbons derived from a sulphur dioxi e extract of mineral oils to a temperature below 450 E. and contacting the hydrocarbons with aluminum chloride, thereby pol erizing said unsaturated constituents while producing arelatively small amount of naphtha, and separating said naphtha from 'the poly- 

